Revealing Nanoscale Molecular Organization in Liquid Crystals via Cryogenic Atom Probe Tomography

TL;DR

This paper introduces cryogenic atom probe tomography (cryo-APT) as a novel method to visualize and analyze the nanoscale molecular organization of liquid crystals, overcoming previous resolution limitations.

Contribution

The study develops a tailored cryogenic FIB protocol and demonstrates cryo-APT's capability to preserve and analyze intact molecules and fragments in liquid crystals at nanoscale resolution.

Findings

Resolved homogeneous mixing of 5CB and 8CB in nematic phase

Observed sub-nanometer crystalline layering in supercooled 8CB

Revealed field-directed dissociation pathways of CB molecules

Abstract

While liquid crystals (LCs) have been extensively studied, obtaining a comprehensive nanoscale picture of their molecular organization remains challenging, as conventional techniques face an intrinsic trade-off between spatial and chemical resolution. Here, cryogenic atom probe tomography (cryo-APT) is introduced as a new analytical approach for LC materials, using 4'-Pentyl-4-cyanobiphenyl (5CB) and 4'-Octyl-4-cyanobiphenyl (8CB) as representative model compounds. This was enabled by a tailored cryogenic focused ion beam (cryo-FIB) protocol optimized for small organic molecules. The method enables controlled field evaporation of both intact molecules and diagnostic fragments, achieving over 90% molecular retention while preserving four characteristic dissociation patterns. By spatially correlating these fragmentation profiles with the local electric field derived from the tip geometry, we reveal field-directed dissociation pathways of CB molecules. In parallel, the distribution of intact molecular ions enables nanoscale visualization of material structure: we resolve homogeneous mixing of 5CB and 8CB in the nematic phase and directly observe the sub-nanometer crystalline layering in a supercooled 8CB sample, with contrast to the surrounding amorphous matrix suggesting the presence of a solid-liquid interface. This work establishes cryo-APT as a new powerful analytical platform for LC research and reveals its broad potential for application in soft matter systems.